In this work, the application of the X-ray multiple diffraction technique using synchrotron radiation at Laboratório Nacional de Luz Síncrotron (LNLS) to study KDP phase transition induced by electric field is discussed. A Huber three-axis (omega, phi, 2theta) diffractometer mounted on a table which rotates around the incident beam allows to measure Renninger scans (RS) at the XRD station of LNLS using the adequate polarization for the experiments. Prior results indicated (080) as the best choice for the KDP primary reflection and the (440)(<img src="http:/img/fbpe/mr/v4n1/quatro.gif" alt="quatro.gif (94 bytes)"> 40) four-beam case for the secondary. Two Bragg-surface diffraction (BSD) reflections, where the secondary beam is propagated parallel to the sample surface, are involved in this multiple diffraction case. A RS interval of 3.3° around phi = 0° position was measured while the electric field was increased up to 6 kV/cm. At this value, a phase transition was observed and the secondary peaks became narrower and changed their RS position indicating possible occurrence of a metastable ferroelectric phase
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